The present invention provides 1-acetyl-3,3-dimethylcyclohexane derivatives having the generic structure: ##STR3## wherein R.sub.1 or one or both of R.sub.2 and/or R.sub.3 is methallyl and the other of R.sub.1 or R.sub.2 and/or R.sub.3 is hydrogen and a straightforward, economical process directed towards synthesizing such 1-acetyl-3,3-dimethylcyclohexane derivatives by reaction of methallyl halides with acetyl-3,3-dimethylcyclohexane, and utilization of such 1-acetyl-3,3-dimethylcyclohexane derivatives for their organoleptic properties in perfumes, perfumed articles, foodstuffs, medicinal products, tobaccos and tobacco articles.
In the perfumery art there is a considerable need for substituents having green, herbaceous, melony and fruity aromas with galbanum-like, ginger-like and citrusy nuances. Specifically described are materials having such a profile but which do not discolor with age. Such fragrance materials have a wide utilization in perfume formulations and perfumed articles. A minimum amount of such materials that give rise to these properties is available from natural sources but the natural materials are subject to wide variations in quality, are expensive, and are limited or often in critically short supply.
Furthermore, there is a continuing search for compositions which can vary, modify, fortify, enhance, augment or otherwise improve the flavor and aroma of foodstuffs, chewing gums and medicinal products. To be satisfactory, such compositions should be stable, non-toxic and blendable with other ingredients to provide its own unique flavor and aroma nuance without detracting from the co-ingredients. Preferably, such compositions should be naturally occurring or present in natural foodstuffs so that their ingestible safety can be readily recognized or, such compositions should be similar to those materials present in natural foodstuffs so that their ingestible safety can be recognized. These materials should be capable of being synthesized in a simple and economical manner. The need for safe flavors in the fruity flavor area, e.g. citrus flavor area, is well-known, particularly in the beverage flavor area and in the yogurt flavor area. More specifically, there is a need for the development of non-toxic materials which can replace natural materials not readily available, having sweet, fruity, citrus, green and vegetable aroma and flavor characteristics.
Firmenich's Dutch published application No. 7500838 discloses the preparation of the compound having the structure: ##STR4## and discloses its use in perfumery and in augmenting foodstuff flavors. The perfumery use of this compound and other members of its class as "floral, green, herbaceous and chypre" useful in galbanum resinoids is also disclosed.
The compounds disclosed in Dutch published application No. 7500838 have organoleptic properties which causes them to be different in kind from 1-acetyl-3,3,-dimethylcyclohexane, which has unobvious, unexpected and advantageous characteristics in the field of augmenting or enhancing the organoleptic impressions of foodstuffs, foodstuff flavors, perfumes, perfumed articles and medicinal products.
Insofar as relevant prior art concerning the process for preparing 1-acetyl-3,3-dimethylcyclohexane is concerned, German Pat. No. 1,244,784, issued on July 20, 1967, discloses the reaction: ##STR5## wherein R can be one of alkyl, alkenyl, allyl, propargyl, cyclohexyl or benzyl; X is chloro or bromo, and R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 can be hydrogen, alkyl, alkenyl or phenyl. The reaction of the German Patent is limited to ketones. However, the nature of the reaction is different in kind from the reaction of the instant invention.
German Pat. No. 1,244,784 corresponds to British Pat. No. 1,059,839 published on Feb. 22, 1967, entitled, "Process for Preparing Ketones and Novel Ketones so Prepared." Tamai, et al, U.S. Pat. No. 3,983,175 issued on Sept. 28, 1976, (a continuation-in-part of Ser. No. 417,201 filed on Nov. 19, 1972, now abandoned) discloses a process for producing a ketone which has a replaceable hydrogen atom on the carbon atom in the alpha position to the carbonyl group in the presence of an aqueous alkali metal hydroxide and a nitrogen-containing base as a catalyst, e.g., primary amines, secondary amines, tertiary amines, and quarternary ammonium salts. The nature of the reaction described in the patent by Tamai et al. is different in kind from the reaction of the instant invention. The same holds true for Meuly, et al., U.S. Pat. No. 3,668,255 issued on June 6, 1972, a continuation-in-part of Ser. No. 241,036 filed Nov. 29, 1962, now abandoned.